10.1002/anie.201814018
Angewandte Chemie International Edition
COMMUNICATION
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Scheme 6. Asymmetric trapping of the silylketene 1a.
In conclusion, we have discovered the first examples of the
Wolff rearrangement by oxidatively generated α-oxo gold
carbene species. The TBS group installed at the terminal alkyne
is essential due to its steric shielding effect and electronic
influence. The generated silylketenes are stable enough to be
isolated or can be trapped by tethered HO groups or various
external nucleophiles to afford γ-lactones, α-silylated carboxylic
acid and their derivatives, or TBS-substituted allenes. The
trapping by thiophenol is also realized asymmetrically. This
strategy avoids the typical use of hazardous diazo ketone
substrates and provides a facile one- or two-step route to
synthetically versatile yet isolable silylketenes from readily
available alkyne substrates. It is anticipated this chemistry would
further advance the applications of silylketene in organic
synthesis.
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Y.Z. thanks the China Scholarship Council for a scholarship. We
thank NIGMS R01GM123342 for financial support and NIH
shared instrument grant S10OD012077 for the purchase of a
400 MHz NMR spectrometer.
Keywords: the Wolff rearrangement • gold catalysis • α-oxo
carbenes • silylketene • alkyne
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